CN108864342B - Binuclear (alpha-diimine) nickel/palladium olefin catalyst and preparation and application thereof - Google Patents

Binuclear (alpha-diimine) nickel/palladium olefin catalyst and preparation and application thereof Download PDF

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CN108864342B
CN108864342B CN201710325708.8A CN201710325708A CN108864342B CN 108864342 B CN108864342 B CN 108864342B CN 201710325708 A CN201710325708 A CN 201710325708A CN 108864342 B CN108864342 B CN 108864342B
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diimine
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傅智盛
邢震艳
范志强
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Zhejiang University ZJU
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    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
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Abstract

The invention relates to the technical field of olefin catalytic polymerization, and aims to provide a binuclear (α -diimine) nickel/palladium olefin catalyst and preparation and application thereofThe application is as follows. The chemical structural formula of the catalyst is shown as formula I or formula II. The molecular structure of the catalyst of the invention is more diversified, the chain structure (such as molecular weight and branching degree) of a polymerization product can be adjusted in a wider range, particularly, the catalyst with asymmetric molecular structure has two active centers with different properties, and the molecular weight and/or branching degree of the respectively generated polymer has obvious difference, so that the catalyst can be used for preparing bimodal distribution type polyolefin and other polyolefin materials with novel structures.

Description

Binuclear (alpha-diimine) nickel/palladium olefin catalyst and preparation and application thereof
Technical Field
The invention belongs to the technical field of olefin catalytic polymerization, and particularly relates to a binuclear (alpha-diimine) nickel/palladium olefin catalyst, and a preparation method and application thereof.
Background
Polyolefin is a basic material related to the national civilization, and is widely applied to various fields of industry, agriculture, national defense and the like due to the excellent performance, various varieties, easily available raw materials, low price and the like. The development and application of new catalysts are one of the core driving forces for the advancement and development of the polyolefin industry, and are the key points for controlling the structure and performance of polyolefin.
The (alpha-diimine) nickel/palladium catalyst can catalyze ethylene polymerization to obtain branched polyethylene. Researchers have made a lot of researches and improvements on the catalysts to obtain a catalytic system with excellent catalytic performance, but most of the researches are directed to mononuclear (alpha-diimine) nickel/palladium catalysts, and research on binuclear or polynuclear catalysts is less.
Chinese patent inventions 200710070354.3, 201210276244.3, 201410024754.0 provide binuclear (α -diimine) nickel/palladium catalysts, respectively. Because the binuclear (alpha-diimine) nickel/palladium catalyst contains two metal centers and a special coordination effect exists between the two active centers, the binuclear (alpha-diimine) nickel/palladium catalyst shows different catalytic performance from the mononuclear (alpha-diimine) nickel/palladium catalyst, and the catalytic activity and the polymer molecular weight can be improved. The existing binuclear (alpha-diimine) nickel/palladium catalysts have a single molecular structure, and the chain structure (such as molecular weight and branching degree) of polyethylene prepared by catalyzing ethylene polymerization by using the catalysts is also relatively single.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a binuclear (alpha-diimine) nickel/palladium olefin catalyst and a preparation method and application thereof.
In order to solve the technical problem, the solution of the invention is as follows:
a binuclear (alpha-diimine) nickel/palladium olefin catalyst is provided, which has a chemical structural formula shown as formula I or formula II:
Figure BDA0001291094180000021
in the above formula, R1Is methyl or isopropyl, R2Is methyl or isopropyl, R3Is H, methyl or from 2R3Consisting of camphyl or naphthyl and derivatives thereof, R4Is H, methyl or from 2R4Consisting of camphyl or naphthyl and derivatives thereof, R5Is methyl, tert-butyl, diphenylmethyl or isopropyl, R6Is methyl, tert-butyl, diphenylmethyl or isopropyl, R7Is methyl, tert-butyl, isopropyl, methoxy, N-dimethyl-amino, Cl, Br, CF3Or NO2，R8Is methyl, tert-butyl, isopropyl, methoxy, N-dimethyl-amino, Cl, Br, CF3Or NO2And X is Cl or Br.
The present invention further provides a process for preparing the aforementioned binuclear (α -diimine) nickel/palladium olefin catalyst, comprising the steps of:
(1) dropwise adding aniline into diketone with the same mole for ketoamine condensation reaction to obtain a compound C1; wherein, the aniline contains substituents R5 and R7, and the diketone contains a substituent R3;
Figure BDA0001291094180000022
(2) dropwise adding aniline into diketone with the same mole for ketoamine condensation reaction to obtain a compound C2; wherein, the aniline contains substituents R6 and R8, and the diketone contains a substituent R4;
Figure BDA0001291094180000031
(3) compound C1 was added dropwise to an equimolar amount of 4, 4' -diamino-3, 3', 5, 5' -tetrasubstituted biphenyl for the ketoamine condensation reaction to give compound C3:
Figure BDA0001291094180000032
(4) and (3) performing ketoamine condensation reaction on the compound C3 and an equimolar compound C2 to obtain a ligand L:
Figure BDA0001291094180000033
(5) respectively reacting the ligand L with (DME) NiBr under the anhydrous and oxygen-free conditions2、NiCl2·6H2O or (COD) PdCH3Cl to obtain the binuclear (α -diimine) nickel/palladium olefin catalyst shown in the formula I or the formula II.
The present invention also provides a binuclear (α -diimine) nickel/palladium olefin catalyst composition comprising, in addition to the binuclear (α -diimine) nickel/palladium olefin catalyst of claim 1, a second component promoter which is Li (Et)2O)2.8B(C6F5)4Any one of methylaluminoxane, diethylaluminum monochloride, ethylaluminum dichloroate or ethylaluminum sesqui.
In the present invention, the binuclear (α -diimine) nickel/palladium olefin catalyst composition further comprises a chain shuttling agent which is any one of trimethylaluminum, triethylaluminum, triisobutylaluminum, dibutylmagnesium, dimethylmagnesium, or diethylzinc.
The invention further provides application of the binuclear (alpha-diimine) nickel/palladium olefin catalyst composition in preparation of polyethylene, polypropylene or ethylene and alpha-olefin copolymer.
Description of the inventive principles:
in the binuclear (α -diimine) nickel/palladium olefin catalyst with the chemical structural formula shown as formula I or formula II, two active centers are connected through a conjugated ligand, and electrons can freely flow through the conjugated structure to enable the two active centers to be in free flowThe two completely different active centers are formed by the difference of the mutual influence. In addition, R7And R8The former may be an electron donating group and the latter may be an electron withdrawing group, as substituents having different electronic effects. This results in a greater difference in the electronegativity of the Ni metal active centers to which they are attached. And R7The linked Ni metal active centers are less electronegative and R8The electronegativity of the connected Ni metal active center is strong. The electronegativity of the Ni metal active center influences the chain structure and molecular weight of the polymer produced by the Ni metal active center. Taking ethylene as an example, the Ni metal active center with strong electronegativity catalyzes ethylene to generate polyethylene with higher branching degree and lower molecular weight, and the Ni metal active center with weak electronegativity catalyzes ethylene to generate polyethylene with lower branching degree and higher molecular weight, so that two different polyethylenes can be obtained by using one catalyst, and the two polyethylenes can be used for preparing bimodal polyethylene. In addition, if a chain shuttling agent is added to the polymerization system, a multi-block polymer in which two polyethylenes having different chain structures are alternately connected can be prepared.
Compared with the prior art, the invention has the beneficial effects that:
the molecular structure of the catalyst of the invention is more diversified, the chain structure (such as molecular weight and branching degree) of a polymerization product can be adjusted in a wider range, particularly, the catalyst with asymmetric molecular structure has two active centers with different properties, and the molecular weight and/or branching degree of the respectively generated polymer has obvious difference, so that the catalyst can be used for preparing bimodal distribution type polyolefin and other polyolefin materials with novel structures.
Detailed Description
The method for preparing the binuclear (alpha-diimine) nickel/palladium olefin catalyst comprises the following steps:
(1) dropwise adding aniline into diketone with the same mole for ketoamine condensation reaction to obtain a compound C1; wherein, the aniline contains substituents R5 and R7, and the diketone contains a substituent R3;
Figure BDA0001291094180000051
(2) dropwise adding aniline into diketone with the same mole for ketoamine condensation reaction to obtain a compound C2; wherein, the aniline contains substituents R6 and R8, and the diketone contains a substituent R4;
Figure BDA0001291094180000052
(3) compound C1 was added dropwise to an equimolar amount of 4, 4' -diamino-3, 3', 5, 5' -tetrasubstituted biphenyl for the ketoamine condensation reaction to give compound C3:
Figure BDA0001291094180000053
(4) and (3) performing ketoamine condensation reaction on the compound C3 and an equimolar compound C2 to obtain a ligand L:
Figure BDA0001291094180000061
(5) respectively reacting the ligand L with (DME) NiBr under the anhydrous and oxygen-free conditions2、NiCl2·6H2O or (COD) PdCH3Cl to give the binuclear (α -diimine) nickel/palladium olefin catalyst of formula I or formula II:
Figure BDA0001291094180000062
in the above formula, R1Is methyl or isopropyl, R2Is methyl or isopropyl, R3Is H, methyl or from 2R3Consisting of camphyl or naphthyl and derivatives thereof, R4Is H, methyl or from 2R4Consisting of camphyl or naphthyl and derivatives thereof, R5Is methyl, tert-butyl, diphenylmethyl or isopropyl, R6Is methyl, tert-butyl, diphenylmethyl or isopropyl, R7Is methyl, tert-butyl, isopropyl, methoxy, N-dimethyl-amino, Cl, Br, CF3Or NO2，R8Is methyl, tert-butyl, isopropyl,Methoxy, N-dimethyl-amino, Cl, Br, CF3Or NO2And X is Cl or Br.
The condensation reaction and coordination reaction of ketone amine involved in the synthesis process of the catalyst are both classic reactions in the literature, and the reaction parameters such as the input amount of reactants and reaction conditions are all universal in the synthesis process, and are well known by researchers in the technical field. The present invention will be further described with reference to the following specific examples, but the present invention is not limited to the following examples. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature.
References chem. eur.j.2002,8(13):2848 and Organometallics,2005,24(6) for the synthesis of 4-substituent-2, 6-diisopropylaniline according to the invention: 1145.
Preparation of ligands
Example 1
Synthesis of ligand L1
The chemical structural formula of ligand L1 is as follows:
Figure BDA0001291094180000071
under nitrogen atmosphere and 85 ℃, 2mmol acenaphthenequinone is added into a three-neck flask containing 80mL acetonitrile, after half an hour, 15mL acetic acid is added, after stirring and dissolving for two hours, 2mmol 4-nitro-2, 6-diisopropylaniline (dissolved in 20mL acetonitrile in advance) is added into the three-neck flask dropwise. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and dried under vacuum at 70 ℃ for 48 hours. The product C1-10.515g was obtained in 75% yield.
2mmol of acenaphthenequinone was added to a three-necked flask containing 80mL of acetonitrile under a nitrogen atmosphere at 85 ℃, after half an hour, 15mL of acetic acid was added, and after stirring and dissolving for two hours, 2mmol of 4- (N, N-dimethyl) amino-2, 6-diisopropylaniline (previously dissolved in 20mL of acetonitrile) was added dropwise to the three-necked flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and dried under vacuum at 70 ℃ for 48 hours. 0.562g of product C1-1' was obtained in 78% yield.
Adding 0.5mmol of 4,4 '-diamino-3, 3', 5,5 '-tetraisopropyl biphenyl into a three-neck flask containing 80mL of acetonitrile under the condition of nitrogen atmosphere and 85 ℃, adding 15mL of acetic acid after half an hour, stirring and dissolving for two hours, dropwise adding 0.5mmol of C1-1 (dissolved in 10mL of ethanol in advance) into the three-neck flask, dropwise adding 0.5mmol of C1-1' (dissolved in 10mL of ethanol in advance) into the three-neck flask after 24 hours, stopping the reaction after 24 hours, standing, naturally cooling, washing and precipitating a product, washing and precipitating the product by using 5 × 50mL of n-heptane, and then drying for 48 hours under vacuum at 70 ℃ to obtain 10.422g of the product ligand L, wherein the yield is 80%.1H-NMR(400MHz,CDCl3,in ppm):8.32～8.38(m,8H,Py-H),7.79(s,4H,Py-H),7.68(s,4H,Ar-H),7.38(s,2H,Ar-H),6.57(s,2H,Ar-H),3.06(s，6H,N(CH3)2),2.87(sept,8H,CH(CH3)2),0.86～1.26(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C72H76N6O2:C,81.82％；H,7.20％；N,7.95％。Found:C,81.85％；H,7.27％；N,7.91％。
ESI-MS:m/z 1057.0([M+H]+)
Example 2
Synthesis of ligand L2
The chemical structural formula of ligand L2 is as follows:
Figure BDA0001291094180000081
2mmol of 2, 3-butanedione was charged into a three-necked flask containing 80mL of acetonitrile under a nitrogen atmosphere at 85 ℃ and after half an hour, 15mL of acetic acid was added thereto, followed by stirring and dissolving for two hours, and 2mmol of 4-trifluoromethyl-2, 6-diisopropylaniline (previously dissolved in 20mL of acetonitrile) was added dropwise to the three-necked flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and dried under vacuum at 70 ℃ for 48 hours. The product C1-20.353 g was obtained in 72% yield.
2mmol of 2, 3-butanedione was charged into a three-necked flask containing 80mL of acetonitrile under a nitrogen atmosphere at 85 ℃ and after half an hour, 15mL of acetic acid was added thereto, followed by stirring and dissolving for two hours, and 2mmol of 4- (N, N-dimethyl) amino-2, 6-diisopropylaniline (previously dissolved in 20mL of acetonitrile) was added dropwise to the three-necked flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and dried under vacuum at 70 ℃ for 48 hours. 0.428g of product C1-2' is obtained with a yield of 82%.
Adding 0.5mmol of 4,4 '-diamino-3, 3', 5,5 '-tetraisopropyl biphenyl into a three-neck flask containing 80mL of acetonitrile under a nitrogen atmosphere at 85 ℃, adding 15mL of acetic acid after half an hour, stirring and dissolving for two hours, dropwise adding 0.5mmol of C1-2 (dissolved in 10mL of ethanol in advance) into the three-neck flask, dropwise adding 0.5mmol of C1-2' (dissolved in 10mL of ethanol in advance) into the three-neck flask after 24 hours, stopping the reaction, standing, naturally cooling, washing the precipitate with 5 × 50mL of n-heptane, and drying under vacuum at 70 ℃ for 48 hours to obtain the product ligand L20.381g with the yield of 85%.1H-NMR(400MHz,CDCl3,in ppm):7.68(s,4H,Ar-H),7.38(s,2H,Ar-H),6.57(s,2H,Ar-H),3.06(s，6H,N(CH3)2),2.87(sept,8H,CH(CH3)2),2.07(s,12H,CCH3),0.86～1.26(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C57H76N5F3:C,76.25％；H,8.47％；N,8.92％。Found:C,76.28％；H,8.41％；N,8.95％。
ESI-MS:m/z 898.0([M+H]+)
Example 3
Synthesis of ligand L3
The chemical structural formula of ligand L3 is as follows:
Figure BDA0001291094180000091
2mmol of glyoxal was charged under nitrogen atmosphere at 85 ℃ into a three-necked flask containing 80mL of acetonitrile, after half an hour, 15mL of acetic acid was added, and after stirring and dissolving for two hours, 2mmol of 4-bromo-2, 6-diisopropylaniline (previously dissolved in 20mL of acetonitrile) was added dropwise into the three-necked flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and dried under vacuum at 70 ℃ for 48 hours. The product C1-30.326g was obtained in 75% yield.
2mmol of glyoxal was charged under nitrogen atmosphere at 85 ℃ into a three-necked flask containing 80mL of acetonitrile, after half an hour, 15mL of acetic acid was added, and after stirring and dissolving for two hours, 2mmol of 4- (N, N-dimethyl) amino-2, 6-diisopropylaniline (previously dissolved in 20mL of acetonitrile) was added dropwise into the three-necked flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and dried under vacuum at 70 ℃ for 48 hours. 0.368g of product C1-3' was obtained with a yield of 79%.
Adding 0.5mmol of 4,4 '-diamino-3, 3', 5,5 '-tetraisopropyl biphenyl into a three-neck flask containing 80mL of acetonitrile under the condition of nitrogen atmosphere and 85 ℃, adding 15mL of acetic acid after half an hour, stirring and dissolving for two hours, dropwise adding 0.5mmol of C1-3 (dissolved in 10mL of ethanol in advance) into the three-neck flask, dropwise adding 0.5mmol of C1-3' (dissolved in 10mL of ethanol in advance) into the three-neck flask after 24 hours, stopping the reaction after 24 hours, standing, naturally cooling, washing and precipitating a product, washing and precipitating the product by using 5 × 50mL of n-heptane, and then drying in vacuum at 70 ℃ for 48 hours to obtain a product ligand L30.362g, wherein the yield is 85%.1H-NMR(400MHz,CDCl3,in ppm):7.68(s,4H,Ar-H),7.50(d,4H,NC-H),7.27(s,2H,Ar-H),6.57(s,2H,Ar-H),3.06(s，6H,N(CH3)2),2.87(sept,8H,CH(CH3)2),0.86～1.26(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C52H68N5Br:C,74.11％；H,8.08％；N,8.31％。Found:C,74.16％；H,8.02％；N,8.38％。
ESI-MS:m/z 843.0([M+H]+)
Example 4
Synthesis of ligand L4
The chemical structural formula of ligand L4 is as follows:
Figure BDA0001291094180000101
2mmol of acenaphthenequinone is added into a three-neck flask containing 80mL of acetonitrile under a nitrogen atmosphere at 85 ℃, after half an hour, 15mL of acetic acid is added, and after stirring and dissolving for two hours, 2mmol of 4-chloro-2, 6-diisopropylaniline (dissolved in 20mL of acetonitrile in advance) is added dropwise into the three-neck flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and dried under vacuum at 70 ℃ for 48 hours. The product C1-40.586g was obtained in 78% yield.
2mmol of acenaphthenequinone was added to a three-neck flask containing 80mL of acetonitrile under nitrogen at 85 ℃, after half an hour, 15mL of acetic acid was added, and after stirring and dissolving for two hours, 2mmol of 4- (N, N-dimethyl) amino-2, 6-dimethylaniline (previously dissolved in 20mL of acetonitrile) was added dropwise to the three-neck flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and dried under vacuum at 70 ℃ for 48 hours. 0.531g of product C1-4' was obtained with a yield of 81%.
Adding 0.5mmol of 4,4 '-diamino-3, 3', 5,5 '-tetramethyl biphenyl into a three-neck flask containing 80mL of acetonitrile under the condition of nitrogen atmosphere and 85 ℃, adding 15mL of acetic acid after half an hour, stirring and dissolving for two hours, dropwise adding 0.5mmol of C1-4 (dissolved in 10mL of ethanol in advance) into the three-neck flask, dropwise adding 0.5mmol of C1-4' (dissolved in 10mL of ethanol in advance) into the three-neck flask after 24 hours, stopping the reaction after 24 hours, standing, naturally cooling, precipitating a product, washing the precipitate with 5 × 50mL of n-heptane, and then drying in vacuum at 70 ℃ for 48 hours to obtain the product ligand L40.351g, wherein the yield is 80%.1H-NMR(400MHz,CDCl3,in ppm):8.32～8.38(m,8H,Py-H),7.79(s,4H,Py-H),7.60(s,4H,Ar-H),7.32(s,2H,Ar-H),6.49(s,,2H,Ar-H),3.06(s，6H,N(CH3)2),2.34(s,18H,CH3),0.86～1.26(dd,12H,CH(CH3)2)。
Elem.Anal.Calcd.For C60H52N5Cl:C,82.05％；H,5.93％；N,7.98％。Found:C,82.08％；H,5.99％；N,7.92％。
ESI-MS:m/z 878.5([M+H]+)
Example 5
Synthesis of ligand L5
The chemical structural formula of ligand L5 is as follows:
Figure BDA0001291094180000111
under the nitrogen atmosphere and at 85 ℃, 2mmol acenaphthenequinone is added into a three-neck flask containing 80mL acetonitrile, after half an hour, 15mL acetic acid is added, after stirring and dissolving for two hours, 2mmol 4-nitro-2, 6-di-tert-butylaniline (dissolved in 20mL acetonitrile in advance) is added into the three-neck flask dropwise. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and then dried under vacuum at 70 ℃ for 48 hours. The product C1-50.645g was obtained in 75% yield.
Under nitrogen atmosphere and 85 ℃, 2mmol acenaphthenequinone is added into a three-neck flask containing 80mL acetonitrile, after half an hour, 15mL acetic acid is added, after stirring and dissolving for two hours, 2mmol 4-methoxy-2, 6-di-tert-butylaniline (dissolved in 20mL acetonitrile in advance) is added into the three-neck flask dropwise. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and dried under vacuum at 70 ℃ for 48 hours. 0.664g of the product C1-5' was obtained with a yield of 80%.
Adding 0.5mmol of 4,4 '-diamino-3, 3', 5,5 '-tetraisopropyl biphenyl into a three-neck flask containing 80mL of acetonitrile under the condition of nitrogen atmosphere and 85 ℃, adding 15mL of acetic acid after half an hour, stirring and dissolving for two hours, dropwise adding 0.5mmol of C1-5 (dissolved in 20mL of ethanol in advance) into the three-neck flask, after 24 hours, dropwise adding 0.5mmol of C1-5' (dissolved in 20mL of ethanol in advance) into the three-neck flask, stopping the reaction after 24 hours, standing, naturally cooling, washing and precipitating a product, washing and precipitating the product by using 5 × 50mL of n-heptane, and then drying for 48 hours under vacuum at 70 ℃ to obtain the product ligand L50.422g, wherein the yield is 80 percent。1H-NMR(400MHz,CDCl3,in ppm):8.32～8.38(m,8H,Py-H),8.15(s,2H,Ar-H),7.79(s,4H,Py-H),7.68(s,4H,Ar-H),7.04(s,2H,Ar-H),3.83(s，3H,OCH3),2.87(sept,4H,CH(CH3)2),1.35(s,36H,C(CH3)3),0.86～1.26(dd,24H,CH(CH3)2)。
Elem.Anal.Calcd.For C77H87N5O3:C,81.84％；H,7.73％；N,6.20％。Found:C,81.88％；H,7.79％；N,6.26％。
ESI-MS:m/z 1130.0([M+H]+)
Example 6
Synthesis of ligand L6
The chemical structural formula of ligand L6 is as follows:
Figure BDA0001291094180000121
2mmol of acenaphthenequinone is added into a three-neck flask containing 80mL of acetonitrile under a nitrogen atmosphere at 85 ℃, after half an hour, 15mL of acetic acid is added, and after stirring and dissolving for two hours, 2mmol of 4-trifluoromethyl-2, 6-diisopropylaniline (dissolved in 20mL of acetonitrile in advance) is added dropwise into the three-neck flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and then dried under vacuum at 70 ℃ for 48 hours. The product C1-60.695 g was obtained in 85% yield.
Under the condition of nitrogen atmosphere and 85 ℃, 0.5mmol of 4, 4' -diamino-3, 3', 5, 5' -tetraisopropyl biphenyl is added into a three-neck flask containing 80mL of acetonitrile, after half an hour, 15mL of acetic acid is added, stirring and dissolving are carried out for two hours, 1mmol of C1-6 (dissolved in 20mL of ethanol in advance) is added into the three-neck flask dropwise, the reaction is stopped after 24 hours, the mixture is stood and naturally cooled, the product is precipitated, the precipitate is washed by 5 × 50mL of n-heptane and is dried in vacuum at 70 ℃ for 48 hours, and the product ligand L60.422g is obtained, the yield is 80%.1H-NMR(400MHz,CDCl3,in ppm):8.32～8.38(m,8H,Py-H),7.79(s,4H,Py-H),7.68(s,4H,Ar-H),7.38(s,4H,Ar-H),2.87(sept,8H,CH(CH3)2),0.86～1.26(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C72H70N4F6:C,78.26％；H,6.34％；N,5.07％。Found:C,78.21％；H,6.37％；N,5.02％。
ESI-MS:m/z 1105.0([M+H]+)
Example 7
Synthesis of ligand L7
The chemical structural formula of ligand L7 is as follows:
Figure BDA0001291094180000122
2mmol of acenaphthenequinone was added to a three-neck flask containing 80mL of acetonitrile under a nitrogen atmosphere at 85 ℃, after half an hour, 15mL of acetic acid was added, and after stirring and dissolving for two hours, 2mmol of 2, 6-diisopropylaniline (previously dissolved in 20mL of acetonitrile) was added dropwise to the three-neck flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and then dried under vacuum at 70 ℃ for 48 hours. The product C1-70.552 g was obtained with a yield of 81%.
Under the condition of nitrogen atmosphere and 85 ℃, 0.5mmol of 4, 4' -diamino-3, 3', 5, 5' -tetraisopropyl biphenyl is added into a three-neck flask containing 80mL of acetonitrile, after half an hour, 15mL of acetic acid is added, stirring and dissolving are carried out for two hours, 1mmol of C1-7 (dissolved in 20mL of ethanol in advance) is added into the three-neck flask dropwise, the reaction is stopped after 24 hours, the mixture is stood and naturally cooled, the product precipitate is separated out, the precipitate is washed by 5 × 50mL of n-heptane, and then vacuum drying is carried out for 48 hours at 70 ℃, and the product ligand L70.402g is obtained, and the yield is 83%.1H-NMR(400MHz,CDCl3,in ppm):8.32～8.38(m,8H,Py-H),7.79(s,4H,Py-H),7.68(s,4H,Ar-H),7.51(s,2H,Ar-H),7.12(s,4H,Ar-H),2.87(sept,8H,CH(CH3)2),0.86～1.26(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C70H72N4:C,86.78％；H,7.44％；N,5.79％。Found:C,86.72％；H,7.48％；N,5.73％。
ESI-MS:m/z 969.0([M+H]+)
Example 8
Synthesis of ligand L8
The chemical structural formula of ligand L8 is as follows:
Figure BDA0001291094180000131
2mmol of 5, 6-dihydrocyclopentyl [ f, g ] acenaphthene-1, 2-dione was added to a three-necked flask containing 80mL of acetonitrile under a nitrogen atmosphere at 85 ℃ and after half an hour, 15mL of acetic acid was added, and after stirring and dissolving for two hours, 2mmol of 2, 6-diisopropylaniline (previously dissolved in 20mL of acetonitrile) was added dropwise to the three-necked flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and then dried under vacuum at 70 ℃ for 48 hours. The product C1-80.609g was obtained in 83% yield.
Under the condition of nitrogen atmosphere and 85 ℃, 0.5mmol of 4, 4' -diamino-3, 3', 5, 5' -tetraisopropyl biphenyl is added into a three-neck flask containing 80mL of acetonitrile, after half an hour, 15mL of acetic acid is added, stirring is carried out, after two hours of dissolution, 1mmol of C1-8 (dissolved in 20mL of ethanol in advance) is added into the three-neck flask dropwise, the reaction is stopped after 24 hours, the mixture is kept stand and naturally cooled, the product is precipitated, the precipitate is washed by 5 × 50mL of n-heptane, and then the precipitate is dried in vacuum at 70 ℃ for 48 hours, and then the product ligand L80.418g is obtained, and the yield is 82%.1H-NMR(400MHz,CDCl3,in ppm):8.32(s,4H,Py-H),7.68(s,4H,Ar-H),7.64(s,4H,Py-H),7.51(s,2H,Ar-H),7.12(s,4H,Ar-H),3.52(t,8H,CH2),2.87(sept,8H,CH(CH3)2),0.86～1.26(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C74H76N4:C,87.06％；H,7.45％；N,5.49％。Found:C,87.02％；H,7.48％；N,5.46％。
ESI-MS:m/z 1021.0([M+H]+)
Example 9
Synthesis of ligand L9
The chemical structural formula of ligand L9 is as follows:
Figure BDA0001291094180000141
2mmol of camphorquinone was added to a three-necked flask containing 80mL of acetonitrile under a nitrogen atmosphere at 85 ℃ and after half an hour, 15mL of acetic acid was added and stirred to dissolve the resulting mixture for two hours, and 2mmol of 2, 6-diisopropylaniline (previously dissolved in 20mL of acetonitrile) was added dropwise to the three-necked flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and then dried under vacuum at 70 ℃ for 48 hours. The product C1-90.358 g was obtained in 55% yield.
Under the condition of nitrogen atmosphere and 85 ℃, 0.5mmol of 4, 4' -diamino-3, 3', 5, 5' -tetraisopropyl biphenyl is added into a three-neck flask containing 80mL of acetonitrile, after half an hour, 15mL of acetic acid is added, stirring is carried out, after two hours of dissolution, 1mmol of C1-9 (dissolved in 20mL of ethanol in advance) is added into the three-neck flask dropwise, the reaction is stopped after 24 hours, standing is carried out, natural cooling is carried out, the product is precipitated, the precipitate is washed by 5 × 50mL of n-heptane, then vacuum drying is carried out at 70 ℃ for 48 hours, and the product ligand L90.411g is obtained, wherein the yield is 85%.1H-NMR(400MHz,CDCl3,in ppm):7.68(s,4H,Ar-H),7.51(s,2H,Ar-H),7.12(s,4H,Ar-H),2.87(sept,8H,CH(CH3)2),1.24～1.49(m,32H,Camph-H)，0.86～1.20(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C68H94N4:C,84.47％；H,9.73％；N,5.80％。Found:C,84.42％；H,9.76％；N,5.83％。
ESI-MS:m/z 967.0([M+H]+)
Example 10
Synthesis of ligand L10
The chemical structural formula of ligand L10 is as follows:
Figure BDA0001291094180000151
under nitrogen atmosphere and 85 ℃, 2mmol of 3, 8-dimethoxy acenaphthene-1, 2-dione is added into a three-neck flask containing 80mL of acetonitrile, after half an hour, 15mL of acetic acid is added, and after stirring and dissolving for two hours, 2mmol of 2, 6-diisopropylaniline (dissolved in 20mL of acetonitrile in advance) is added dropwise into the three-neck flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and then dried under vacuum at 70 ℃ for 48 hours. The product C1-100.69 g was obtained with a yield of 86%.
Under the condition of nitrogen atmosphere and 85 ℃, 0.5mmol of 4, 4' -diamino-3, 3', 5, 5' -tetraisopropyl biphenyl is added into a three-neck flask containing 80mL of acetonitrile, after half an hour, 15mL of acetic acid is added, stirring and dissolving are carried out for two hours, 1mmol of C1-10 (dissolved in 20mL of ethanol in advance) is added into the three-neck flask dropwise, the reaction is stopped after 24 hours, the mixture is stood and naturally cooled, the product is precipitated, the precipitate is washed by 5 × 50mL of n-heptane and is dried in vacuum at 70 ℃ for 48 hours, and the product ligand L100.452g is obtained, and the yield is 83%.1H-NMR(400MHz,CDCl3,in ppm):8.32～8.38(m,8H,Py-H),7.79(s,4H,Py-H),7.68(s,4H,Ar-H),7.51(s,2H,Ar-H),7.12(s,4H,Ar-H),2.87(sept,8H,CH(CH3)2),0.86～1.26(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C74H80N4O4:C,81.62％；H,7.35％；N,5.15％。Found:C,81.66％；H,7.32％；N,5.19％。
ESI-MS:m/z 1089.0([M+H]+)
Example 11
Synthesis of ligand L11
The chemical structural formula of ligand L11 is as follows:
Figure BDA0001291094180000152
2mmol of cyclopentyl [ f, g ] acenaphthylene-1, 2-dione was added to a three-necked flask containing 80mL of acetonitrile under a nitrogen atmosphere at 85 ℃, after half an hour, 15mL of acetic acid was added, and after stirring and dissolving for two hours, 2mmol of 2, 6-diisopropylaniline (previously dissolved in 20mL of acetonitrile) was added dropwise to the three-necked flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and then dried under vacuum at 70 ℃ for 48 hours. The product C1-110.609 g was obtained in 83% yield.
Under the condition of nitrogen atmosphere and 85 ℃, 0.5mmol of 4, 4' -diamino-3, 3', 5, 5' -tetraisopropyl biphenyl is added into a three-neck flask containing 80mL of acetonitrile, after half an hour, 15mL of acetic acid is added, stirring is carried out, after two hours of dissolution, 1mmol of C1-11 (dissolved in 20mL of ethanol in advance) is added into the three-neck flask dropwise, the reaction is stopped after 24 hours, standing is carried out, natural cooling is carried out, product precipitate is separated out, the precipitate is washed by 5 × 50mL of n-heptane, and then vacuum drying is carried out at 70 ℃ for 48 hours, thus obtaining the product ligand L110.427g, the yield is 84%.1H-NMR(400MHz,CDCl3,in ppm):8.22(s,4H,Py-H),7.68(s,4H,Ar-H),7.64(s,4H,Py-H),7.51(s,2H,Ar-H),7.15(s,4H,C-H),7.12(s,4H,Ar-H),2.87(sept,8H,CH(CH3)2),0.86～1.26(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C74H72N4:C,87.40％；H,7.09％；N,5.51％。Found:C,87.45％；H,7.15％；N,5.58％。
ESI-MS:m/z 1017.0([M+H]+)
Example 12
Synthesis of ligand L12
The chemical structural formula of ligand L12 is as follows:
Figure BDA0001291094180000161
2mmol of 5, 6-dimethyl acenaphthylene-1, 2-dione was added to a three-necked flask containing 80mL of acetonitrile under a nitrogen atmosphere at 85 ℃, after half an hour, 15mL of acetic acid was added, and after stirring and dissolving for two hours, 2mmol of 2, 6-diisopropylaniline (previously dissolved in 20mL of acetonitrile) was added dropwise to the three-necked flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and then dried under vacuum at 70 ℃ for 48 hours. The product C1-120.649 g was obtained with a yield of 88%.
Under the nitrogen atmosphere and the temperature of 85 ℃, 0.5mmol of 4, 4' -diamino-3, 3', 5, 5' -tetraisopropyl biphenyl was added into a three-necked flask containing 80mL of acetonitrile, after half an hour, 15mL of acetic acid was added, after stirring and dissolving for two hours, 1mmol of C1-12 (previously dissolved in 20mL of ethanol) was added dropwise into the three-necked flask, after 24 hours the reaction was stopped, the mixture was allowed to stand, and naturally cooled, and the product was precipitated, washed with 5 × 50mL of n-heptane, and then vacuum-dried at 70 ℃ for 48 hours, to obtain the product ligand L120.440g, with a yield of 86%.1H-NMR(400MHz,CDCl3,in ppm):8.22(s,4H,Py-H),7.68(s,4H,Ar-H),7.51(s,2H,Ar-H),7.23(s,4H,Py-H),7.12(s,4H,Ar-H),2.87(sept,8H,CH(CH3)2),0.86～1.26(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C74H80N4:C,86.63％；H,7.80％；N,5.46％。Found:C,86.66％；H,7.88％；N,5.42％。
ESI-MS:m/z 1025.0([M+H]+)
Example 13
Synthesis of ligand L13
The chemical structural formula of ligand L13 is as follows:
Figure BDA0001291094180000171
2mmol of glyoxal was charged under nitrogen atmosphere at 85 ℃ into a three-necked flask containing 80mL of acetonitrile, after half an hour, 15mL of acetic acid was added, and after stirring and dissolving for two hours, 2mmol of 2, 6-diisopropylaniline (previously dissolved in 20mL of acetonitrile) was added dropwise into the three-necked flask. Stopping the reaction after 24 hours, standing, naturally cooling, and precipitating and separating out a product. The precipitate was washed with 5X 50mL of n-heptane and then dried under vacuum at 70 ℃ for 48 hours. The product C1-130.369 g was obtained in 75% yield.
0.5mmol of 4, 4' -diamino-3, 3', 5, 5' -tetraisopropyl biphenyl was added to a three-necked flask containing 80mL of acetonitrile under a nitrogen atmosphere at 85 ℃ and after half an hour, 15mL of acetic acid was added thereto, and after stirring and dissolving for two hours, 0.5mmol of C1-13 (previously dissolved in 20mL of ethanol) was added dropwise to the three-necked flask. After 24 hours, 0.5mmol of C1-7 (previously dissolved in 20mL of ethanol)) Dropping the mixture into a three-neck flask, stopping the reaction after 24 hours, standing, naturally cooling, precipitating a product, washing the precipitate with 5 × 50mL of n-heptane, and then drying in vacuum at 70 ℃ for 48 hours to obtain 50.346 g of a product ligand L, wherein the yield is 82%.1H-NMR(400MHz,CDCl3,in ppm):8.32～8.38(m,4H,Py-H),7.79(s,2H,Py-H),7.68(s,4H,Ar-H),7.51(s,2H,Ar-H)，7.50(d,2H,CH),7.12(s,4H,Ar-H),2.87(sept,8H,CH(CH3)2),0.86～1.26(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C60H66N4:C,85.51％；H,7.84％；N,6.65％。Found:C,85.55％；H,7.81％；N,6.69％。
ESI-MS:m/z 843.0([M+H]+)
The diketone (or aldehyde) compounds with various types are condensed with aniline with different types, and the condensation products are respectively reacted with 4, 4' -diamino-3, 3', 5, 5' -tetra-substituted biphenyl to obtain ligands with different molecular structures. As the reaction process and the reaction conditions are different, the specific preparation methods of various ligands are not listed.
Preparation of di-and binuclear (alpha-diimine) palladium complexes
Example 14
Synthesis of catalyst Pd1
0.2mmol of ligand L1 and 0.4mmol of 1, 5-cyclooctadienemethyl palladium chloride were added to a 50mL Schlenk flask (under a nitrogen atmosphere), and 20mL of methylene chloride was injected and stirred at 23 ℃ for 24 hours. After the reaction, the mixture was allowed to stand, the solution was filtered, and the filtrate was then vacuum-dried to remove methylene chloride. The solid powder was then washed with 4X 10mL of diethyl ether and dried under vacuum at room temperature for 10 hours to give 0.246g of solid powder in 90% yield.
1H-NMR(400MHz,CDCl3,in ppm):8.32～8.38(m,8H,Py-H),7.79(s,4H,Py-H),7.68(s,4H,Ar-H),7.38(s,2H,Ar-H),6.57(s,,2H,Ar-H),3.06(s，6H,N(CH3)2),2.87(sept,8H,CH(CH3)2),0.86～1.26(dd,48H,CH(CH3)2)，0.50～0.80(s,6H,Pd-CH3)。
Elem.Anal.Calcd.For C74H82N6O2Pd2Cl2:C,64.86％；H,5.99％；N,6.14％。Found:C,64.81％；H,6.05％；N,6.18％。
ESI-MS:m/z 1370.0([M+H]+)
Example 15
Synthesis of catalyst Pd7
0.2mmol of ligand L7 and 0.4mmol of 1, 5-cyclooctadienemethyl palladium chloride were added to a 50mL Schlenk flask (under a nitrogen atmosphere), and 20mL of methylene chloride was injected and stirred at 23 ℃ for 24 hours. After the reaction, the mixture was allowed to stand, the solution was filtered, and the filtrate was then vacuum-dried to remove methylene chloride. The solid powder was then washed with 4X 10mL of diethyl ether and dried under vacuum at room temperature for 10 hours to give 0.236g of solid powder in 92% yield.
1H-NMR(400MHz,CDCl3,in ppm):8.32～8.38(m,8H,Py-H),7.79(s,4H,Py-H),7.68(s,4H,Ar-H),7.51(s,2H,Ar-H),7.12(s,4H,Ar-H),2.87(sept,8H,CH(CH3)2),0.86～1.26(dd,48H,CH(CH3)2),0.50～0.80(s,6H,Pd-CH3)。
Elem.Anal.Calcd.For C72H78N4Pd2Cl2:C,67.45％；H,6.09％；N,4.37％。Found:C,67.48％；H,6.01％；N,4.32％。
ESI-MS:m/z 1282.0([M+H]+)
Example 16
Synthesis of catalyst Pd13
0.2mmol of ligand L13 and 0.4mmol of 1, 5-cyclooctadienemethyl palladium chloride were added to a 50mL Schlenk flask (under nitrogen atmosphere), 20mL of dichloromethane was injected, and the mixture was stirred at 23 ℃ for 24 hours, after the reaction was completed, the mixture was allowed to stand, the solution was filtered, the filtrate was subjected to vacuum suction to remove dichloromethane, and then the solid powder was washed with 4 × 10mL of diethyl ether and vacuum-dried at room temperature for 10 hours to obtain 0.215g of solid powder, yield 93%.1H-NMR(400MHz,CDCl3,in ppm):8.32～8.38(m,4H,Py-H),7.79(s,2H,Py-H),7.68(s,4H,Ar-H),7.51(s,2H,Ar-H)，7.50(d,2H,CH),7.12(s,4H,Ar-H),2.87(sept,8H,CH(CH3)2),0.86～1.26(dd,48H,CH(CH3)2),0.50～0.80(s,6H,Pd-CH3)。
Elem.Anal.Calcd.For C62H72N4Pd2Cl2:C,64.42％；H,6.23％；N,4.85％。Found:C,64.47％；H,6.25％；N,4.81％。
ESI-MS:m/z 1156.0([M+H]+)
Complexing various ligands and 1, 5-cyclooctadiene methyl palladium chloride to obtain various binuclear (alpha-diimine) palladium complexes. As the reaction process and the reaction conditions are different, the specific preparation methods of various binuclear (alpha-diimine) palladium complexes are not listed.
Preparation of tri-and binuclear (alpha-diimine) nickel complex
Example 17
Synthesis of catalyst Ni1
0.4mmol of (DME) NiBr2Was added to a 50mL single-necked round bottom flask (under nitrogen) and 10mL of methylene chloride was poured and stirred to give a pale yellow suspension. 0.2mmol of ligand L1 was added to a 50mL Schlenk flask (nitrogen atmosphere) and 10mL of dichloromethane were injected. Injecting into (DME) NiBr with injector2The reaction was stopped by stirring for 24 hours at 23 ℃ and standing, the lower layer was precipitated, the solution was filtered, the filtrate was dried under reduced pressure to remove methylene chloride, the solid powder was washed with 4 × 15mL of diethyl ether and dried under vacuum at room temperature for 10 hours to give 0.281g of solid powder in 94% yield, Elem72H76N6O2Ni2Br4C, 57.91%; h, 5.09%; and N,5.63 percent. Found C, 57.95%; h, 5.02%; and N,5.68 percent. The content of metallic nickel in the complex, determined by ICP, was 7.95%, theoretical 7.91%.
In an infrared spectrum, the characteristic absorption peak of stretching vibration of a ligand in a C ═ N double bond is mainly 1630-1665 cm-1. The characteristic absorption peak of the stretching vibration of the C ═ N double bond in the complex is obviously shifted to low wave number (1615-1650 cm)-1) It can be seen that effective coordination occurs between the nitrogen atom and the metallic nickel atomA bit.
Example 18
Synthesis of catalyst Ni7
0.4mmol of (DME) NiBr2Was added to a 50mL single-necked round bottom flask (under nitrogen) and 10mL of methylene chloride was poured and stirred to give a pale yellow suspension. 0.2mmol of ligand L7 was added to a 50mL Schlenk flask (nitrogen atmosphere) and 10mL of dichloromethane were injected. Injecting into (DME) NiBr with injector2The reaction was stopped by stirring for 24 hours at 23 ℃ and standing, the lower layer was precipitated, the solution was filtered, the filtrate was dried under reduced pressure to remove methylene chloride, the solid powder was washed with 4 × 15mL of diethyl ether and dried under vacuum at room temperature for 10 hours to give 0.253g of solid powder, yield 90%, Elem70H72N4Ni2Br459.74 percent of C; h, 5.12%; and N, 3.98%. Found C, 59.79%; h, 5.18%; n,3.92 percent. The content of metallic nickel in the complex, determined by ICP, was 8.35%, theoretical 8.39%.
In an infrared spectrum, the characteristic absorption peak of stretching vibration of a ligand in a C ═ N double bond is mainly 1630-1665 cm-1. The characteristic absorption peak of the stretching vibration of the C ═ N double bond in the complex is obviously shifted to low wave number (1615-1650 cm)-1) Thus, it can be seen that effective coordination occurs between the nitrogen atom and the metallic nickel atom.
Example 19
Synthesis of catalyst Ni13
0.4mmol of (DME) NiBr2Was added to a 50mL single-necked round bottom flask (under nitrogen) and 10mL of methylene chloride was poured and stirred to give a pale yellow suspension. 0.2mmol of ligand L13 was added to a 50mL Schlenk flask (nitrogen atmosphere) and 10mL of dichloromethane were injected. Injecting into (DME) NiBr with injector2The reaction was stopped by washing the remaining ligand with 5mL of dichloromethane after about 5min of completion, stirring at 23 ℃ for 24 hours, standing, precipitating the lower layer with a little precipitate, filtering the solution, removing dichloromethane by suction drying the filtrate under reduced pressure, washing the solid powder with 4 × 15mL of diethyl ether, vacuum drying at room temperature for 10 hours to obtain 0.236g of solid powder,the yield was 92%. Elem, anal, calcd, for C60H66N4Ni2Br4C,56.25 percent; h, 5.16%; n,4.38 percent. Found is C, 56.21%; h, 5.19%; n,4.32 percent. The content of metallic nickel in the complex, determined by ICP, was 9.31%, theoretical 9.22%.
In an infrared spectrum, the characteristic absorption peak of stretching vibration of a ligand in a C ═ N double bond is mainly 1630-1665 cm-1. The characteristic absorption peak of the stretching vibration of the C ═ N double bond in the complex is obviously shifted to low wave number (1615-1650 cm)-1) Thus, it can be seen that effective coordination occurs between the nitrogen atom and the metallic nickel atom.
Example 20
Synthesis of catalyst Ni13
0.4mmol of NiCl2·6H2O was added to a 50mL single-necked round-bottomed flask (under a nitrogen atmosphere), and 10mL of methylene chloride was introduced and stirred. 0.2mmol) of L13 was added to a 50mL Schlenk flask (nitrogen atmosphere) and 10mL of dichloromethane were injected. Injecting it into NiCl by syringe2·6H2About 5min after the completion of the injection in O suspension, washing the remaining ligand with 5mL of dichloromethane, stirring at 23 ℃ for 24 hours to stop the reaction, standing, precipitating the lower layer with a little precipitate, filtering the solution, vacuum-drying the filtrate under reduced pressure to remove dichloromethane, washing the solid powder with 4 × 15mL of diethyl ether, and vacuum-drying at room temperature for 10 hours to obtain 0.207g of solid powder with a yield of 94% in Elem60H66N4Ni2Cl4C,65.28 percent; h, 5.98%; and N,5.08 percent. Found C, 65.21%; h, 5.92%; n, 5.01%%. The content of metallic nickel in the complex, determined by ICP, was 10.61%, theoretical 10.70%.
In an infrared spectrum, the characteristic absorption peak of stretching vibration of a ligand in a C ═ N double bond is mainly 1630-1665 cm-1. The characteristic absorption peak of the stretching vibration of the C ═ N double bond in the complex is obviously shifted to low wave number (1615-1650 cm)-1) Thus, it can be seen that effective coordination occurs between the nitrogen atom and the metallic nickel atom.
Various types of ligands with (DME) NiBr2Or NiCl2·6H2O goes on to get rid ofVarious binuclear (α -diimine) nickel complexes can be obtained through synthesis, and specific preparation methods of various binuclear (α -diimine) nickel complexes are not listed because the reaction process and the reaction conditions are different.
Four, two-core (alpha-diimine) palladium catalyst for catalyzing ethylene polymerization reaction
Example 21
Ethylene pressure polymerization was carried out in a 100mL stainless steel polymerization kettle. Mu. mol of catalyst Pd1 and 20. mu. mol of cocatalyst (Li (Et)2O)2.8B(C6F5)4) Dissolving in 10mL of dichloromethane, injecting the dichloromethane solution at room temperature and ethylene pressure of 0.2MPa, polymerizing for 20 hours, dropping the polymer solution into methanol or acetone solution rapidly by using a rubber head dropper for precipitation, filtering the polymer, washing with methanol or acetone for several times, drying in vacuum at 50 ℃ to constant weight, weighing 8.11g of polymer, wherein the catalyst activity is 2.03 × 104g[mol(Pd)h]-1The weight average molecular weight of the GPC peak 1 of the polymerization product was 349.1kg/mol, the polydispersity was 2.0, and the weight average molecular weight of the peak 2 was 5.5kg/mol, the polydispersity was 1.9.1The degree of branching of the polymer was determined by H-NMR to be 118/1000 carbon atoms.
Example 22
Ethylene pressure polymerization was carried out in a 100mL stainless steel polymerization kettle. Mu. mol of catalyst Pd7 and 20. mu. mol of cocatalyst (Li (Et)2O)2.8B(C6F5)4) Dissolving in 10mL of dichloromethane, injecting the dichloromethane solution at room temperature and ethylene pressure of 0.2MPa, polymerizing for 20 hours, dropping the polymer solution into methanol or acetone solution rapidly by using a rubber head dropper for precipitation, filtering the polymer, washing with methanol or acetone for several times, drying in vacuum at 50 ℃ to constant weight, weighing to obtain 7.99g of polymer, wherein the catalyst activity is 2.0 × 104g[mol(Pd)h]-1The weight average molecular weight of GPC Peak 1 of the polymerization product was 289.1kg/mol, the polydispersity was 2.1, the weight average molecular weight of Peak 2 was 7.5kg/mol, and the polydispersity was 1.8.1The degree of branching of the polymer was determined by H-NMR to be 109/1000 carbon atoms.
Example 23
Ethylene pressure polymerization was carried out in a 100mL stainless steel polymerization kettle. Mu. mol of catalyst Pd13 and 20. mu. mol of cocatalyst (Li (Et)2O)2.8B(C6F5)4) Dissolving in 10mL of dichloromethane, injecting the dichloromethane solution at room temperature and ethylene pressure of 0.2MPa, polymerizing for 20 hours, dropping the polymer solution into methanol or acetone solution rapidly by using a rubber head dropper for precipitation, filtering the polymer, washing with methanol or acetone for several times, drying in vacuum at 50 ℃ to constant weight, weighing to obtain 7.69g of polymer, wherein the catalyst activity is 1.92 × 104g[mol(Pd)h]-1The weight average molecular weight of GPC Peak 1 of the polymerization product was 275.2kg/mol, the polydispersity was 2.04, and the weight average molecular weight of Peak 2 was 6.8kg/mol, the polydispersity was 1.79.1The degree of branching of the polymer was determined by H-NMR to be 100/1000 carbon atoms.
Five, binuclear (alpha-diimine) nickel catalyst for catalyzing ethylene polymerization
Example 24
Ethylene atmospheric polymerization is carried out under anhydrous and oxygen-free conditions, 40mL of methylene chloride is injected into a 100mL Schlenk flask at room temperature and ethylene pressure of 0.1MPa, 2mmol of cocatalyst methylaluminoxane is then injected into the methylene chloride, 5. mu. mol of main catalyst Ni1 is dissolved in 10mL of methylene chloride and injected into the Schlenk flask, after half an hour of polymerization, the polymer solution is rapidly dropped into a methanol or acetone solution by using a rubber-headed dropper for precipitation, the polymer is filtered, then washed several times with methanol or acetone, dried under vacuum at 50 ℃ to constant weight, and 2.65g of polymer is weighed, the catalyst activity is 5.30 × 105g[mol(Ni)h]-1The weight average molecular weight of GPC Peak 1 of the polymerization product was 248.6kg/mol, the polydispersity was 2.2, and the weight average molecular weight of Peak 2 was 64.3kg/mol, the polydispersity was 1.9.1The degree of branching of the polymer was determined by H-NMR to be 78/1000 carbon atoms.
Example 25
The atmospheric polymerization of ethylene is carried out under anhydrous and oxygen-free conditions. 40mL of methylene chloride was injected into a 100mL Schlenk flask at room temperature and an ethylene pressure of 0.1MPa, and then 2mmol of cocatalyst methylaluminoxane was injected thereto.Dissolving 5 mu mol of main catalyst Ni7 in 10mL of dichloromethane, injecting the solution into a Schlenk bottle, polymerizing for half an hour, rapidly dropping the polymer solution into a methanol or acetone solution by using a rubber head dropper for precipitation, filtering the polymer, washing the polymer for a plurality of times by using methanol or acetone, drying the polymer in vacuum at 50 ℃ to constant weight, weighing 2.36g of polymer, wherein the catalyst activity is 4.72 × 105g[mol(Ni)h]-1The weight average molecular weight of the GPC peak 1 of the polymerization product was 215.4kg/mol, the polydispersity was 2.4, and the weight average molecular weight of the GPC peak 2 was 53.4kg/mol, and the polydispersity was 2.2.1The degree of branching of the polymer was determined by H-NMR to be 72/1000 carbon atoms.
Example 26
Ethylene atmospheric polymerization was carried out under anhydrous and oxygen-free conditions at room temperature and ethylene pressure of 0.1MPa, 40mL of methylene chloride was charged into a 100mL Schlenk flask, followed by charging 2mmol of methylaluminoxane as a cocatalyst, 5. mu. mol of Ni13 as a main catalyst was dissolved in 10mL of methylene chloride, which was charged into a Schlenk flask, after half an hour of polymerization, the polymer solution was rapidly dropped into a methanol or acetone solution with a rubber-tipped dropper for precipitation, the polymer was filtered, then washed several times with methanol or acetone, vacuum-dried at 50 ℃ to constant weight, and 2.12g of the polymer was weighed, the catalyst activity was 4.24 × 105g[mol(Ni)h]-1The weight average molecular weight of GPC Peak 1 of the polymerization product was 189.3kg/mol, the polydispersity was 2.2, and the weight average molecular weight of Peak 2 was 51.8kg/mol, the polydispersity was 2.4.1The degree of branching of the polymer was determined by H-NMR to be 71/1000 carbon atoms.
Example 27
Ethylene atmospheric polymerization was carried out under anhydrous and oxygen-free conditions at room temperature and ethylene pressure of 0.1MPa, 40mL of methylene chloride was charged into a 100mL Schlenk flask, followed by charging 2mmol of methylaluminoxane as a cocatalyst, 5. mu. mol of Ni 13' as a main catalyst was dissolved in 10mL of methylene chloride, which was charged into a Schlenk flask, after half an hour of polymerization, the polymer solution was rapidly dropped into a methanol or acetone solution with a rubber-tipped dropper for precipitation, the polymer was filtered, then washed several times with methanol or acetone, vacuum-dried at 50 ℃ to constant weight, and 2.14g of the polymer was weighed, the catalyst activity was 4.28 × 105g[mol(Ni)h]-1The weight average molecular weight of GPC Peak 1 of the polymerization product was 189.8kg/mol, the polydispersity was 2.2, and the weight average molecular weight of Peak 2 was 51.6kg/mol, the polydispersity was 2.4.1The degree of branching of the polymer was determined by H-NMR to be 71/1000 carbon atoms.
Example 28
The cocatalyst was changed to diethylaluminum chloride, the other conditions were the same as in example 25. 5.76g of polymer was obtained, and the catalyst activity was 1.15 × 106g[mol(Ni)h]-1The weight average molecular weight of the GPC peak 1 of the polymerization product was 173.6kg/mol, the polydispersity was 2.2, and the weight average molecular weight of the GPC peak 2 was 71.9kg/mol, and the polydispersity was 1.9.1The degree of branching of the polymer was determined by H-NMR to be 79/1000 carbon atoms.
Example 29
The cocatalyst was changed to ethylaluminum dichloride under the same conditions as in example 25 except that the polymer treatment method was changed to obtain 7.54g of a polymer, and the catalyst activity was 1.51 × 106g[mol(Ni)h]-1The weight average molecular weight of GPC Peak 1 of the polymerization product was 154.6kg/mol, the polydispersity was 2.3, and the weight average molecular weight of Peak 2 was 53.8kg/mol, the polydispersity was 2.1.1The degree of branching of the polymer was determined by H-NMR to be 82/1000 carbon atoms.
Example 30
The cocatalyst was changed to ethylaluminum sesqui, the other conditions were the same as in example 25. 7.15g of polymer was obtained, the catalyst activity was 1.43 × 106g[mol(Ni)h]-1The weight average molecular weight of GPC Peak 1 of the polymerization product was 172.9kg/mol, the polydispersity was 2.1, and the weight average molecular weight of Peak 2 was 66.9kg/mol, the polydispersity was 2.2.1The degree of branching of the polymer was determined by H-NMR to be 81/1000 carbon atoms.
Example 31
The atmospheric polymerization of ethylene is carried out under anhydrous and oxygen-free conditions. 40mL of methylene chloride was injected into a 100mL Schlenk flask at room temperature and an ethylene pressure of 0.1MPa, followed by injection of 2mmol of methylaluminoxane as a cocatalyst, and further injection of 0.1mmol of trimethylaluminum as a chain shuttling agent. Mu. mol of Ni1 as a main catalyst was dissolved in 10mL of methylene chloride and injected into ScAfter polymerization for half an hour in a hlenk flask, the polymer solution is quickly dripped into a methanol or acetone solution by a rubber head dropper for precipitation, the polymer is filtered, washed for a plurality of times by methanol or acetone, dried in vacuum at 50 ℃ to constant weight and weighed to obtain 2.59g of polymer with the catalyst activity of 5.18 × 105g[mol(Ni)h]-1The weight-average molecular weight of the polymerization product was 218.7kg/mol, and the polydispersity was 2.5.1The degree of branching of the polymer was determined by H-NMR to be 71/1000 carbon atoms.
Example 32
The chain shuttling agent was changed to triethylaluminum, the other conditions were the same as the polymer treatment method in example 31, 2.38g of a polymer was obtained, and the catalyst activity was 4.76 × 105g[mol(Ni)h]-1The weight-average molecular weight of the polymerization product was 213.9kg/mol, and the polydispersity was 2.6.1The degree of branching of the polymer was determined by H-NMR to be 73/1000 carbon atoms.
Example 33
The chain shuttling agent was changed to triisobutylaluminum and the other conditions were the same as in example 31. 2.53g of a polymer, catalyst activity was 5.06 × 105g[mol(Ni)h]-1The weight-average molecular weight of the polymerization product was 222.3kg/mol, and the polydispersity was 2.5.1The degree of branching of the polymer was determined by H-NMR to be 72/1000 carbon atoms.
Example 34
The chain shuttling agent was changed to dibutylmagnesium under the same conditions and polymer processing method as in example 31 to give 2.45g of polymer and a catalyst activity of 4.9 × 105g[mol(Ni)h]-1The weight-average molecular weight of the polymerization product was 216.8kg/mol, and the polydispersity was 2.4.1The degree of branching of the polymer was determined by H-NMR to be 70/1000 carbon atoms.
Example 35
The chain shuttling agent was changed to dimethylmagnesium, the other conditions were the same as in example 31 except that the polymer treatment method was used, 2.59g of polymer was obtained, and the catalyst activity was 5.18 × 105g[mol(Ni)h]-1The weight-average molecular weight of the polymerization product was 225.8kg/mol, and the polydispersity was 2.6.1The degree of branching of the polymer was determined by H-NMR to be 73/1000 carbon atoms.
Example 36
The chain shuttling agent was changed to diethyl zinc and the other conditions were the same as in example 31. 2.53g of polymer was obtained, the catalyst activity was 5.06 × 105g[mol(Ni)h]-1The weight-average molecular weight of the polymerization product was 225.3kg/mol, and the polydispersity was 2.5.1The degree of branching of the polymer was determined by H-NMR to be 73/1000 carbon atoms.
Six, binuclear (alpha-diimine) nickel catalyst for catalyzing alpha-olefin homopolymerization and copolymerization with ethylene
Example 37
The copolymerization of ethylene and 1-dodecene is carried out under the condition of no water and no oxygen, under the condition of room temperature and ethylene pressure of 0.1MPa, 40mL of toluene is injected into 100mL of Schlenk bottle, 3.3mL of 1-dodecene is injected, 2mmol of cocatalyst methylaluminoxane is injected into the toluene, 5 mu mol of main catalyst Ni1 is dissolved by 10mL of toluene and injected into the Schlenk bottle, after half an hour of polymerization, the polymer solution is quickly dropped into the methanol or acetone solution by a rubber head dropper for precipitation, the polymer is filtered, then the polymer is washed for a plurality of times by methanol or acetone, the polymer is dried in vacuum at 50 ℃ to constant weight and weighed to obtain 2.09g of polymer, the activity of the catalyst is 4.18 × 105g[mol(Ni)h]-1The weight-average molecular weight of the polymerization product was 225.6kg/mol, and the polydispersity was 2.1. The enthalpy of fusion was 24.5J/g, melting point-43.3 ℃ as determined by DSC.
Example 38
The polymerization was carried out with the addition of 4.5mL of 1-octadecene, under the same conditions as in example 28 except that the polymer treatment method was the same as that of example 28. 2.07g of a polymer was obtained. the catalyst activity was 4.14 × 105g[mol(Ni)h]-1The weight-average molecular weight of the polymerization product was 225.5kg/mol, and the polydispersity was 2.2. The enthalpy of fusion was 40.2J/g, melting point-18.3 ℃ as determined by DSC.
Example 39
The polymerization was carried out with the addition of 9.6mL of 1-octadecene, under the same conditions as in example 28 except that the polymer treatment method was the same as that of example 28. 2.31g of a polymer was obtained. the catalyst activity was 4.62 × 105g[mol(Ni)h]-1The weight average molecular weight of the polymerization product was 231.3kg/mol, polydispersity 2.0. The enthalpy of fusion, determined by DSC, was 65.4J/g, the melting point was 2.7 ℃.
Example 40
The polymerization was carried out with the addition of 14.4mL of 1-octadecene, under the same conditions as in example 28 except that the polymer treatment method was the same as that of example 28. 2.78g of a polymer was obtained. the catalyst activity was 5.56 × 105g[mol(Ni)h]-1The weight-average molecular weight of the polymerization product was 242.5kg/mol, and the polydispersity was 2.2. The enthalpy of fusion, determined by DSC, was 60.4J/g, the melting point was 6.3 ℃.
EXAMPLE 41
The propylene pressure polymerization is carried out in a 100mL stainless steel polymerizer, 40mL toluene is injected into the stainless steel polymerizer at room temperature and propylene pressure of 0.4MPa, 2mmol of cocatalyst methylaluminoxane is then injected into the polymerizer, 5 mu mol of main catalyst Ni1 is dissolved in 10mL toluene, the main catalyst Ni1 is injected into the stainless steel polymerizer, after polymerization for half an hour, the polymerizer is decompressed and opened, the polymer solution is rapidly dropped into methanol or acetone solution by a rubber head dropper for precipitation, the polymer is filtered, then washed by methanol or acetone for several times, and then dried in vacuum at 50 ℃ to constant weight and weighed to obtain 0.65g of polymer, the catalyst activity is 1.3 × 105g[mol(Ni)h]-1The weight-average molecular weight of the polymerization product was 156.2kg/mol, and the polydispersity was 2.6.1The degree of branching of the polymer was determined by H-NMR to be 271/1000 carbon atoms.

Claims (3)

1. A preparation method of a binuclear (alpha-diimine) nickel/palladium olefin catalyst is characterized by comprising the following steps:
(1) dropwise adding aniline into diketone with the same mole for ketoamine condensation reaction to obtain a compound C1; wherein, the aniline contains substituents R5 and R7, and the diketone contains a substituent R3;
Figure FDA0002535984970000011
(2) dropwise adding aniline into diketone with the same mole for ketoamine condensation reaction to obtain a compound C2; wherein, the aniline contains substituents R6 and R8, and the diketone contains a substituent R4;
Figure FDA0002535984970000012
(3) compound C1 was added dropwise to an equimolar amount of 4, 4' -diamino-3, 3', 5, 5' -tetrasubstituted biphenyl for the ketoamine condensation reaction to give compound C3:
Figure FDA0002535984970000013
(4) and (3) performing ketoamine condensation reaction on the compound C3 and an equimolar compound C2 to obtain a ligand L:
Figure FDA0002535984970000021
(5) respectively reacting the ligand L with (DME) NiBr under the anhydrous and oxygen-free conditions2、NiCl2·6H2O or (COD) PdCH3Cl to give the binuclear (α -diimine) nickel/palladium olefin catalyst of formula I or formula II:
Figure FDA0002535984970000022
in the above formula, R1Is methyl or isopropyl, R2Is methyl or isopropyl, R3Is H, methyl or from 2R3Consisting of camphyl or naphthyl and derivatives thereof, R4Is H, methyl or from 2R4Consisting of camphyl or naphthyl and derivatives thereof, R5Is methyl, tert-butyl, diphenylmethyl or isopropyl, R6Is methyl, tert-butyl, diphenylmethyl or isopropyl, R7Is methyl, tert-butyl, isopropyl, methoxy, N-dimethyl-amino, Cl, Br, CF3Or NO2，R8Is methyl, tert-butyl, isopropyl, methoxy, N-dimethyl-amino, Cl, Br, CF3Or NO2And X is Cl or Br.
2. A dinuclear (α -diimine) nickel/palladium olefin catalyst composition comprising, in addition to the dinuclear (α -diimine) nickel/palladium olefin catalyst of claim 1, a second component cocatalyst which is Li (Et) and a chain shuttling agent2O)2.8B(C6F5)4Any one of methylaluminoxane, diethylaluminum monochloride, ethylaluminum dichloroate or ethylaluminum sesqui; the chain shuttling agent is any one of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, dibutyl magnesium, dimethyl magnesium or diethyl zinc.
3. Use of the dinuclear (α -diimine) nickel/palladium olefin catalyst composition of claim 2 in the preparation of polyethylene, polypropylene or copolymers of ethylene and α -olefins.
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